CN111448229B - (meth) acrylic-modified polyester resin, curable resin composition, coating material, and coated steel sheet - Google Patents
(meth) acrylic-modified polyester resin, curable resin composition, coating material, and coated steel sheet Download PDFInfo
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- CN111448229B CN111448229B CN201780097073.9A CN201780097073A CN111448229B CN 111448229 B CN111448229 B CN 111448229B CN 201780097073 A CN201780097073 A CN 201780097073A CN 111448229 B CN111448229 B CN 111448229B
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
- C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/16—Dicarboxylic acids and dihydroxy compounds
- C08G63/18—Dicarboxylic acids and dihydroxy compounds the acids or hydroxy compounds containing carbocyclic rings
- C08G63/181—Acids containing aromatic rings
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
- C08F283/02—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polycarbonates or saturated polyesters
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
- C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/16—Dicarboxylic acids and dihydroxy compounds
- C08G63/20—Polyesters having been prepared in the presence of compounds having one reactive group or more than two reactive groups
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/91—Polymers modified by chemical after-treatment
- C08G63/914—Polymers modified by chemical after-treatment derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/916—Dicarboxylic acids and dihydroxy compounds
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D151/00—Coating compositions based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers
- C09D151/08—Coating compositions based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers grafted on to macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
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Abstract
The present invention provides a (meth) acrylic modified polyester resin, characterized in that a saturated polyester resin (a) and a (meth) acrylic monomer mixture (B) are used as essential reaction raw materials, the (meth) acrylic monomer mixture (B) contains a hydroxyl group-containing (meth) acrylic monomer, the saturated polyester resin (a) is a polycondensate of an aliphatic diol (a 1) and a dicarboxylic acid (a 2) containing an aliphatic dicarboxylic acid, and the content of the aliphatic dicarboxylic acid in the dicarboxylic acid (a 2) is 5 mass% or more. The (meth) acrylic modified polyester resin can realize high solidification of the coating material and can form a coating film having excellent processability and weather resistance.
Description
Technical Field
The present invention relates to a (meth) acrylic modified polyester resin, a curable resin composition containing the same, a coating material containing the curable resin composition, and a coated steel sheet having a coating film of the coating material.
Background
As a method for coating various metal parts or metal formed products for home appliances, automobile parts, building materials, can-making applications, etc., a pre-coating method of coating a steel sheet in advance, and a post-coating method of forming a steel sheet and then coating the formed steel sheet are known. Steel sheets used in the precoating method are generally called precoat metals (hereinafter, abbreviated as "PCM"), and since steel sheets coated in advance are cut according to the application and are used by forming into various shapes, PCM coatings are required to have extremely high workability and weather resistance in addition to hardness and gloss of the coating film surface.
In recent years, in consideration of the influence on the environment, studies have been made on a high-solid PCM coating having a reduced amount of Volatile Organic Compounds (VOCs) and a low solvent content, and the coating has been required to have a high solid content.
Conventional PCM coatings have used various forms of coatings such as two-component curable type, ultraviolet curable type, and volatile dry type, and various resin systems such as polyester resin, fluororesin, and acrylic resin, but among these, two-component curable coatings mainly composed of polyester resin have been widely used in view of excellent processability.
As the two-component curable coating material containing a polyester resin as a main component, for example, a coating material containing a polyester resin having a number average molecular weight (Mn) of 11,000 as a reaction raw material, such as terephthalic acid, isophthalic acid, 2-methyl-1,3-propanediol, 1,6-hexanediol, is known (for example, see patent document 1), and although the coating material has excellent processability, it has not reached the standard required in recent years in terms of high solid content of the coating material.
Therefore, a material capable of forming a coating film having excellent processability and weather resistance while achieving high solidification of the coating material is required.
Documents of the prior art
Patent document
Patent document 1: japanese patent laid-open publication No. 9-12969
Disclosure of Invention
Problems to be solved by the invention
The problem to be solved by the present invention is to provide a (meth) acrylic modified polyester resin which can realize high solidification of a coating and can form a coating film having excellent processability and weather resistance, a curable resin composition containing the same, a coating, and a coated steel sheet.
Means for solving the problems
The present inventors have made intensive studies to solve the above problems, and as a result, have found that the above problems can be solved by using a (meth) acrylic modified polyester resin using a saturated polyester resin and a (meth) acrylic monomer mixture as essential reaction raw materials, and have completed the present invention.
That is, the present invention relates to a (meth) acrylic modified polyester resin characterized by comprising, as essential reaction raw materials, a saturated polyester resin (a) and a (meth) acrylic monomer mixture (B) containing a hydroxyl group-containing (meth) acrylic monomer, wherein the saturated polyester resin (a) is a condensation product of an aliphatic diol (a 1) and an aliphatic dicarboxylic acid-containing dicarboxylic acid (a 2), and the content of the aliphatic dicarboxylic acid in the dicarboxylic acid (a 2) is 5% by mass or more, a curable resin composition, a coating material, and a coated steel sheet containing the same.
ADVANTAGEOUS EFFECTS OF INVENTION
The (meth) acrylic modified polyester resin of the present invention can realize high solid content of a coating material, i.e., high non-volatile differentiation, and can form a coating film having excellent processability and weather resistance, and therefore, can be suitably used for automotive coatings such as PCM coatings, automotive top-coat coatings, and automotive refinish coatings. The term "high solids" as used herein means that the nonvolatile content of the coating material is 65% by mass or more.
Detailed Description
The (meth) acrylic modified polyester resin of the present invention is characterized in that a saturated polyester resin (a) and a (meth) acrylic monomer mixture (B) are used as essential reaction raw materials.
The saturated polyester resin (A) is a polyester resin having substantially no aliphatic double bonds between carbon atoms.
The saturated polyester resin (a) is obtained by polycondensation of an aliphatic diol (a 1) and a dicarboxylic acid (a 2).
The aliphatic diol (a 1) preferably contains an asymmetric diol having at least 1 side chain and/or a linear diol having no side chain, from the viewpoint of obtaining a (meth) acrylic-modified polyester resin which can realize high solidification of a coating material and can form a coating film having excellent processability and weather resistance. The term "asymmetric diol" as used herein means a diol having an asymmetric structure.
Examples of the asymmetric diol having at least 1 side chain include 2-butyl-2-ethyl-1,3-propanediol, 2-methyl-1,4-butanediol, 2-ethyl-1,4-butanediol, 2-methyl-1,3-propanediol, 3-methyl-1,5-pentanediol, and 3-methyl-1,5-heptanediol. These asymmetric diols having at least 1 side chain may be used alone, or 2 or more kinds may be used in combination. Among these, 2-methyl-1,3-propanediol is preferred.
Examples of the linear diol having no side chain include ethylene glycol, diethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol, 1,8-octanediol, 1,9-nonanediol, 1,10-dodecanediol, 1,11-undecanediol, 1,12-dodecanediol, 1,13-tridecanediol, 1,14-tetradecanediol, 1,15-pentadecanediol, 1,16-hexadecanediol, 1,17-heptadecanediol, 1,18-octadecanediol, 1,19-nonadecanediol, and 1,20. These straight chain diols having no side chain may be used alone, or 2 or more kinds may be used in combination. Among these, 1,6-hexanediol is preferred from the viewpoint of obtaining a (meth) acrylic modified polyester resin which can realize high solidification of a coating material and can form a coating film having excellent processability and weather resistance.
In addition, as the aliphatic diol (a 1), in addition to the asymmetric diol having at least 1 side chain and the linear diol having no side chain, other diols may be used as necessary.
Examples of the other aliphatic diols include neopentyl glycol, hydrogenated bisphenol A, hydrogenated bisphenol F, propylene glycol, dipropylene glycol, 1,3-butanediol, 1,2-butanediol, 1,3-butanediol, 1,2-pentanediol, 1,3-pentanediol, 1,2-hexanediol, 1,4-hexanediol, 2,3-hexanediol, 2,2-diethyl-1,3-propanediol, 1,4-cyclohexanedimethanol, and 1,4-cyclohexanediol. These other aliphatic diols may be used alone, or 2 or more of them may be used in combination.
The dicarboxylic acid (a 2) contains an aliphatic dicarboxylic acid as an essential component in order to obtain a (meth) acrylic modified polyester resin capable of forming a coating film having excellent processability and weather resistance.
Examples of the aliphatic dicarboxylic acid include succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, decanedicarboxylic acid, cyclohexanedicarboxylic acid, dimer acid, fumaric acid, and the like, and methyl esters and acid chlorides of these aliphatic dicarboxylic acids. These aliphatic dicarboxylic acids may be used alone or in combination of 2 or more. Among these, adipic acid is preferable.
The content of the aliphatic dicarboxylic acid is 5% by mass or more, and more preferably 10 to 20% by mass in the dicarboxylic acid (a 2) from the viewpoint of excellent compatibility with the (meth) acrylic monomer mixture (B).
The dicarboxylic acid (a 2) may contain an alicyclic dicarboxylic acid, an aromatic dicarboxylic acid, or an acid anhydride thereof, as necessary. Examples of the alicyclic dicarboxylic acid include 1,3-cyclopentanedicarboxylic acid and 1,4-cyclohexanedicarboxylic acid. Examples of the aromatic dicarboxylic acid include terephthalic acid, isophthalic acid, phthalic acid, naphthalenedicarboxylic acid, diphenyldicarboxylic acid, 1,2-bis (phenoxy) ethane-p, p' -dicarboxylic acid, p-hydroxybenzoic acid, p- (2-hydroxyethoxy) benzoic acid, trimellitic acid, pyromellitic acid, and phthalic anhydride.
In the polycondensation reaction between the aliphatic diol (a 1) and the dicarboxylic acid (a 2), an esterification catalyst may be used, if necessary.
Examples of the esterification catalyst include metal salts such as titanium, tin, zinc, aluminum, zirconium, magnesium, hafnium, and germanium; and metal compounds such as titanium tetraisopropoxide, titanium tetrabutoxide, titanyl acetylacetonate, dibutyltin oxide, dibutyltin diacetate, dibutyltin dilaurate, tin octylate, tin 2-ethylhexanoate, zinc acetylacetonate, zirconium tetrachloride tetrahydrofuran complex, hafnium tetrachloride tetrahydrofuran complex, germanium oxide, and tetraethoxygermanium.
The reaction between the aliphatic diol (a 1) and the dicarboxylic acid (a 2) may be carried out, for example, in the absence of a solvent or in the presence of an organic solvent.
In addition, even when the reaction between the aliphatic diol (a 1) and the dicarboxylic acid (a 2) is carried out in the absence of a solvent, the aliphatic diol may be used after being dissolved in an organic solvent.
Examples of the organic solvent include ketone solvents such as methyl ethyl ketone, acetone, and isobutyl ketone; cyclic ether solvents such as tetrahydrofuran and dioxolane; ester solvents such as methyl acetate, ethyl acetate, and butyl acetate; aromatic solvents such as toluene, xylene, solvent naphtha and the like; alicyclic solvents such as cyclohexane and methylcyclohexane; alcohol solvents such as carbitol, cellosolve, methanol, isopropanol, butanol, propylene glycol monomethyl ether, and the like; glycol ether solvents such as alkylene glycol monoalkyl ether, dialkylene glycol monoalkyl ether, and dialkylene glycol monoalkyl ether acetate. These organic solvents may be used alone, or 2 or more of them may be used in combination.
The weight average molecular weight of the saturated polyester resin (a) is preferably in the range of 1,000 to 5,000, more preferably in the range of 2,000 to 3,000, from the viewpoint of obtaining a (meth) acrylic modified polyester resin which can realize high solidification of a coating material and can form a coating film having excellent processability and weather resistance.
The weight average molecular weight of the saturated polyester resin (a) is a value measured by a Gel Permeation Chromatography (GPC) method.
The (meth) acrylic monomer mixture (B) contains a hydroxyl group-containing (meth) acrylic monomer as an essential component.
Examples of the hydroxyl group-containing (meth) acrylic monomer include (meth) acrylic monomers having a hydroxyl group in the molecule, such as 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, and mono (meth) acrylate of glycerin. These hydroxyl group-containing (meth) acrylic monomers may be used alone or in combination of 2 or more.
The content of the hydroxyl group-containing (meth) acrylic monomer is preferably 10% by mass or more in the (meth) acrylic monomer mixture. In particular, when the (meth) acrylic modified polyester resin of the present invention is used for industrial coatings for automobiles, heavy equipment, and the like, the range of 20 to 40% by mass is more preferable, and when the resin is used for PCM coatings and the like, the range of 10 to 25% by mass is more preferable.
The (meth) acrylic monomer mixture may contain a (meth) acrylic monomer other than the hydroxyl group-containing (meth) acrylic monomer.
Examples of the other (meth) acrylic monomer include alkyl (meth) acrylates such as methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, t-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, hexyl (meth) acrylate, cyclohexyl (meth) acrylate, octyl (meth) acrylate, nonyl (meth) acrylate, dodecyl (meth) acrylate, stearyl (meth) acrylate, isobornyl (meth) acrylate, dicyclopentanyl (meth) acrylate, phenyl (meth) acrylate, and benzyl (meth) acrylate; carboxyl group-containing (meth) acrylic monomers such as (meth) acrylic acid, (. Beta. -carboxyethyl (meth) acrylate), 2- (meth) acryloylpropionic acid, crotonic acid, itaconic acid, maleic acid, fumaric acid, itaconic acid half ester, maleic anhydride, itaconic anhydride, (. Beta.) -acryloyloxyethylsuccinate, (. Beta.) -hydroxyethylphthalate, and salts thereof; amide group-containing (meth) acrylic monomers such as aminoethyl (meth) acrylate, N-monoalkylaminoalkyl (meth) acrylate, N-dialkylaminoalkyl (meth) acrylate, (meth) acrylamide, N-methyl (meth) acrylamide, N-ethyl (meth) acrylamide, N-propylacrylamide, diacetone (meth) acrylamide, N-methylol (meth) acrylamide, N-isopropyl (meth) acrylamide, N-butyl (meth) acrylamide, N-dimethyl (meth) acrylamide, and N, N-diethyl (meth) acrylamide; vinyl ester compounds such as acrolein, vinyl acetate, vinyl propionate, and vinyl versatate; vinyl ether compounds such as methyl vinyl ether, ethyl vinyl ether, propyl vinyl ether, butyl vinyl ether, pentyl vinyl ether and hexyl vinyl ether; vinyl nitrile compounds such as (meth) acrylonitrile; vinyl monomers having an aromatic ring such as styrene, α -methylstyrene, vinyltoluene, vinylanisole, α -halostyrene, and vinylnaphthalene; vinyl monomers having no functional group such as isoprene, butadiene, and ethylene; heterocyclic vinyl monomers such as N-vinylpyrrolidone; phosphoric acid group-containing (meth) acrylic monomers such as (meth) acryloyloxyethyl phosphate, di (meth) acryloyloxyethyl phosphate, tri (meth) acryloyloxyethyl phosphate, and caprolactone-modified (meth) acryloyloxyethyl phosphate. These other (meth) acrylic monomers may be used alone or in combination of 2 or more.
The mass ratio [ (a)/(B) ] of the saturated polyester resin (a) to the (meth) acrylic monomer mixture (B) is preferably in the range of 15/85 to 50/50, more preferably in the range of 25/75 to 35/65, from the viewpoint of obtaining a (meth) acrylic modified polyester resin which can realize high solidification of a coating material and can form a coating film having excellent processability and weather resistance.
The (meth) acrylic modified polyester resin of the present invention can be obtained, for example, by reacting the (meth) acrylic monomer mixture (B) and a polymerization initiator dropwise into an organic solvent solution of the saturated polyester resin (a).
Examples of the polymerization initiator include azo compounds such as 2,2 '-azobis (isobutyronitrile), 2,2' -azobis (2-methylbutyronitrile) and azobiscyanovaleric acid; organic peroxides such as t-butyl peroxypivalate, t-butyl peroxybenzoate, t-butyl peroxy-2-ethylhexanoate, di-t-butyl peroxide, cumene hydroperoxide, benzoyl peroxide, t-butyl hydroperoxide, and t-butyl peroxy-2-ethylhexyl monocarbonate; hydrogen peroxide, ammonium persulfate, potassium persulfate, sodium persulfate, and other inorganic peroxides. These polymerization initiators may be used alone, or 2 or more kinds thereof may be used in combination.
The weight average molecular weight of the (meth) acrylic modified polyester resin of the present invention is preferably in the range of 5,000 to 20,000, more preferably in the range of 7,500 to 12,500, from the viewpoint of obtaining a (meth) acrylic modified polyester resin which can realize high solidification of a coating material and can form a coating film having excellent processability and weather resistance.
The hydroxyl value of the (meth) acrylic polyester resin of the present invention is preferably in the range of 60 to 150 in order to obtain a (meth) acrylic modified polyester resin which can realize high solidification of a coating material and can form a coating film having excellent processability and weather resistance. In particular, when the (meth) acrylic modified polyester resin of the present invention is used for industrial coatings for automobiles, heavy equipment, and the like, the range of 100 to 150 is more preferable, and when the resin is used for PCM coatings and the like, the range of 60 to 100 is more preferable.
The curable resin composition of the present invention contains the (meth) acrylic-modified polyester resin and a curing agent as essential components.
The curing agent may contain a component capable of undergoing a curing reaction with the (meth) acrylic modified polyester resin of the present invention, and examples of such a component include amino resins, polyisocyanate resins, resol resins, epoxy resins, and the like. These may be used alone, or 2 or more of them may be used in combination. The components of the curing agent are appropriately selected depending on the use of the curable resin composition, the use environment, the desired physical properties of the cured product, and the like, and when any curing agent is used as the main agent, the effect of the present invention that provides a cured coating film having an excellent balance between processability and weather resistance can be sufficiently exhibited.
Examples of the amino resin include methylolated amino resins synthesized from at least 1 selected from the group consisting of melamine, urea, and benzoguanamine, and formaldehyde; and those obtained by alkyl-etherifying a part or all of the methylol groups of the methylolated amino resin with a lower monohydric alcohol such as methanol, ethanol, propanol, isopropanol, butanol or isobutanol.
Examples of commercially available products of the amino resin include "Cymel 303" (methylated melamine resin), "Cymel 350" (methylated melamine resin), "U-VAN 520" (n-butylated modified melamine resin), "U-VAN20-SE-60" (n-butylated modified melamine resin), "U-VAN 2021" (n-butylated modified melamine resin), "U-VAN 220" (n-butylated modified melamine resin), "U-VAN 22R" (n-butylated modified melamine resin), "U-VAN 2028" (n-butylated modified melamine resin), "U-VAN 165" (isobutylated modified melamine resin), "U-VAN 114" (isobutylated modified melamine resin), "U-VAN 62" (isobutylated modified melamine resin), and "U-VAN 60R" (isobutylated modified melamine resin), which are manufactured by Allnex. When these amino resins are used, an acid compound such as a phosphoric acid ester may be added as a curing accelerator.
Examples of the polyisocyanate resin include aliphatic diisocyanate compounds such as butane diisocyanate, hexamethylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, and 2,4,4-trimethylhexamethylene diisocyanate; alicyclic diisocyanate compounds such as norbornane diisocyanate, isophorone diisocyanate, hydrogenated xylylene diisocyanate, and hydrogenated diphenylmethane diisocyanate; aromatic diisocyanate compounds such as tolylene diisocyanate, xylylene diisocyanate, tetramethylxylylene diisocyanate, diphenylmethane diisocyanate, 1,5-naphthalene diisocyanate; polymethylene polyphenyl polyisocyanate having a repeating structure described by the following structural formula (1); and isocyanurate-modified products, biuret-modified products, allophanate-modified products, blocked polyisocyanate resins, and the like.
[ in the formula, R 1 Each independently represents a hydrogen atom or a hydrocarbon group having 1 to 6 carbon atoms. R 2 Each independently is carbonAny one of an alkyl group having 1 to 4 atoms or a bonding site connected to the structural site represented by the structural formula (1) via a methylene group with a mark. m is 0 or an integer of 1 to 3, and l is an integer of 1 or more.]
Examples of the epoxy resin include polyglycidyl ethers of polyhydric alcohol compounds, polyglycidyl esters of polycarboxylic acid compounds, bisphenol-type epoxy resins, and novolac-type epoxy resins.
The curable resin composition of the present invention may contain, if necessary, a curing catalyst, a curing accelerator, a pigment dispersant, a matting agent, a leveling agent, a drying inhibitor, an ultraviolet absorber, an antifoaming agent, a thickener, an anti-settling agent, an organic solvent, and the like. The blending ratio of each component and the kind of the blend may be appropriately adjusted depending on the use and desired performance of the curable resin composition. The curable resin composition of the present invention may be of one-pack type or two-pack type. When the curable resin composition of the present invention is a two-pack type, the various additives may be added to either the main agent or the curing agent or both.
The curable resin composition of the present invention can be used in the applications of paints and adhesives, and particularly can be suitably used as a paint for coating steel plates such as automotive paints including PCM paints, automotive top-coat paints, and automotive refinish paints, in view of forming a cured coating film having excellent processability and weather resistance.
The coated steel sheet of the present invention is a coated steel sheet having a cured coating film containing a coating material of the curable resin composition on the surface of a steel sheet, and examples of the steel sheet include a galvanized steel sheet, a plated steel sheet such as an aluminum-zinc alloy steel sheet, a zinc-aluminum-magnesium alloy plated steel sheet, an aluminum alloy sheet, an electromagnetic steel sheet, a copper sheet, a stainless steel sheet, and the like.
Examples
The present invention will be specifically described below with reference to examples and comparative examples.
The number average molecular weight (Mn) and the weight average molecular weight (Mw) of the saturated polyester resin used in the present invention and the number average molecular weight (Mn) and the weight average molecular weight (Mw) of the (meth) acrylic modified polyester resin of the present invention represent values measured by a Gel Permeation Chromatography (GPC) method under the following conditions.
A measuring device: high-efficiency GPC apparatus (HLC-8220 GPC, manufactured by Tosoh corporation)
Column: the following columns, manufactured by Tosoh corporation, were connected in series and used.
"TSK gel G5000" (7.8mmI.D.. Times.30 cm). Times.1 roots
"TSK gel G4000" (7.8mmI.D.. Times.30 cm). Times.1 roots
"TSK gel G3000" (7.8mmI.D.. Times.30 cm). Times.1 roots
"TSK gel G2000" (7.8mmI.D.. Times.30 cm). Times.1 roots
A detector: RI (differential refractometer)
Column temperature: 40 deg.C
Eluent: tetrahydrofuran (THF)
Flow rate: 1.0 mL/min
Injection amount: 100 μ L (tetrahydrofuran solution with a sample concentration of 0.4 mass%)
Standard sample: the calibration curve was prepared using the following standard polystyrene.
(Standard polystyrene)
TSK gel Standard polystyrene A-500 manufactured by Tosoh corporation "
TSK gel Standard polystyrene A-1000 manufactured by Tosoh corporation "
TSK gel Standard polystyrene A-2500, manufactured by Tosoh corporation "
TSK gel Standard polystyrene A-5000 manufactured by Tosoh corporation "
TSK gel standard polystyrene F-1 manufactured by Tosoh corporation "
TSK gel standard polystyrene F-2 manufactured by Tosoh corporation "
TSK gel standard polystyrene F-4 manufactured by Tosoh corporation "
TSK gel standard polystyrene F-10 manufactured by Tosoh corporation "
TSK gel standard polystyrene F-20 manufactured by Tosoh corporation "
TSK gel standard polystyrene F-40 manufactured by Tosoh corporation "
TSK gel standard polystyrene F-80 manufactured by Tosoh corporation "
TSK gel standard polystyrene F-128 manufactured by Tosoh corporation "
TSK gel standard polystyrene F-288 manufactured by Tosoh corporation "
TSK gel standard polystyrene F-550 manufactured by Tosoh corporation "
Production example 1 production of saturated polyester resin (1) solution
5 parts by mass of 2-methyl-1,3-propanediol, 8.95 parts by mass of 1,6-hexanediol, 4 parts by mass of trimethylolpropane, 28.29 parts by mass of neopentyl glycol, 44.76 parts by mass of isophthalic acid, 9 parts by mass of adipic acid, and 0.01 part by mass of tetraisopropyl orthotitanate were put into a reaction vessel equipped with a stirrer, a condenser, and a thermometer. The esterification reaction was carried out at 200 to 250 ℃ for 12 hours while stirring under a nitrogen gas flow to obtain a saturated polyester resin (1). The saturated polyester resin (1) had a number average molecular weight (Mn) of 1,094, a weight average molecular weight (Mw) of 2,114, an acid value of 2.8mgKOH/g, and a hydroxyl value of 137mgKOH/g.
The saturated polyester resin (1) thus obtained was dissolved in butyl acetate to obtain a saturated polyester resin (1) solution having a nonvolatile content of 81.4 mass%. The solution of the saturated polyester resin (1) has a Gardner viscosity of Z4 to Z5.
Production example 2 production of saturated polyester resin (2) solution
15.59 parts by mass of 2-methyl-1,3-propanediol, 10.25 parts by mass of 1,6-hexanediol, 1.97 parts by mass of trimethylolpropane, 17.64 parts by mass of neopentyl glycol, 44.3 parts by mass of isophthalic acid, 10.25 parts by mass of adipic acid, and 0.01 part by mass of tetraisopropyl orthotitanate were put into a reaction vessel equipped with a stirrer, a condenser, and a thermometer. The esterification reaction was carried out at 200 to 250 ℃ for 12 hours while stirring under a nitrogen gas flow to obtain a saturated polyester resin (2). The saturated polyester resin (2) had a number average molecular weight (Mn) of 988, a weight average molecular weight (Mw) of 2,026, an acid value of 2.1mgKOH/g, and a hydroxyl value of 141.3mgKOH/g.
The saturated polyester resin (2) thus obtained was dissolved in butyl acetate to obtain a saturated polyester resin (2) solution having a nonvolatile content of 83.1 mass%. The solution of the saturated polyester resin (2) has a Gardner viscosity of Z3 to Z4.
Production example 3 production of saturated polyester resin (3) solution
30 parts by mass of 2-methyl-1,3-propanediol, 10 parts by mass of 1,6-hexanediol, 1 part by mass of trimethylolpropane, 4 parts by mass of neopentyl glycol, 35 parts by mass of isophthalic acid, 20 parts by mass of adipic acid and 0.01 part by mass of tetraisopropyl orthotitanate were put into a reaction vessel equipped with a stirrer, a condenser and a thermometer. The esterification reaction was carried out at 200 to 250 ℃ for 12 hours while stirring under a nitrogen gas stream to obtain a saturated polyester resin (3). The saturated polyester resin (3) had a number average molecular weight (Mn) of 667, a weight average molecular weight (Mw) of 1,441, an acid value of 7.2mgKOH/g, and a hydroxyl value of 169.2mgKOH/g.
The saturated polyester resin (3) obtained above was dissolved in butyl acetate to obtain a saturated polyester resin (3) solution having a nonvolatile content of 87 mass%. The solution of the saturated polyester resin (3) has a Gardner viscosity of Z2 to Z3.
Production example 4 production of saturated polyester resin (4) solution
23.32 parts by mass of 2-methyl-1,3-propanediol, 3.89 parts by mass of 1,6-hexanediol, 1.94 parts by mass of trimethylolpropane, 12.05 parts by mass of neopentyl glycol, 45.19 parts by mass of isophthalic acid, 13.61 parts by mass of adipic acid, and 0.01 part by mass of tetraisopropyl orthotitanate were put into a reaction vessel equipped with a stirrer, a condenser, and a thermometer. The esterification reaction was carried out at 200 to 250 ℃ for 12 hours while stirring under a nitrogen gas stream to obtain a saturated polyester resin (4). The saturated polyester resin (4) had a number average molecular weight (Mn) of 2,149, a weight average molecular weight (Mw) of 4,968, an acid value of 4.7mgKOH/g, and a hydroxyl value of 78.6mgKOH/g.
The saturated polyester resin (4) thus obtained was dissolved in a mixed solvent of 800 parts by mass of an aromatic solvent ("Solvesso 100" manufactured by Exxon Mobil co., ltd.) and 200 parts by mass of propylene glycol monomethyl ether acetate to obtain a saturated polyester resin (4) solution having a nonvolatile content of 78.3% by mass. The saturated polyester resin (4) solution has a Gardner viscosity of Z-Z1.
Production example 5 production of saturated polyester resin (5) solution
30.81 parts by mass of 2-methyl-1,3-propanediol, 6.85 parts by mass of 1,6-hexanediol, 1.17 parts by mass of trimethylolpropane, 4.25 parts by mass of neopentyl glycol, 38.44 parts by mass of isophthalic acid, 18.49 parts by mass of adipic acid, and 0.01 part by mass of tetraisopropyl orthotitanate were put into a reaction vessel equipped with a stirrer, a condenser, and a thermometer. The esterification reaction was carried out at 200 to 250 ℃ for 12 hours while stirring under a nitrogen gas flow to obtain a saturated polyester resin (5). The saturated polyester resin (5) had a number average molecular weight (Mn) of 1,234, a weight average molecular weight (Mw) of 2,998, an acid value of 6mgKOH/g, and a hydroxyl value of 113.5mgKOH/g.
The saturated polyester resin (5) thus obtained was dissolved in butyl acetate to obtain a saturated polyester resin (5) solution having a nonvolatile content of 82.2 mass%. The saturated polyester resin (5) solution has a Gardner viscosity of X-Y.
Production example 6 production of saturated polyester resin (6) solution
25.76 parts by mass of 2-methyl-1,3-propanediol, 2.02 parts by mass of trimethylolpropane, 12.63 parts by mass of neopentyl glycol, 40.4 parts by mass of isophthalic acid, 16.67 parts by mass of terephthalic acid, 2.53 parts by mass of adipic acid and 0.01 part by mass of tetraisopropyl orthotitanate were put into a reaction vessel equipped with a stirrer, a condenser and a thermometer. The esterification reaction was carried out at 200 to 250 ℃ for 12 hours while stirring under a nitrogen gas flow to obtain a saturated polyester resin (6). The saturated polyester resin (6) had a number average molecular weight (Mn) of 1,763, a weight average molecular weight (Mw) of 4,028, an acid value of 4.5mgKOH/g, and a hydroxyl value of 94.4mgKOH/g.
The saturated polyester resin (6) obtained above was dissolved in butyl acetate to obtain a saturated polyester resin (6) solution having a nonvolatile content of 72 mass%. The saturated polyester resin (6) solution has a Gardner viscosity of Z1 to Z2.
( Example 1: preparation of (meth) acrylic-modified polyester resin (1) solution )
17.41 parts by mass of the saturated polyester resin (1) solution obtained in production example 1 and 20.38 parts by mass of butyl acetate were charged into a reaction vessel equipped with a stirrer, a condenser and a thermometer, and the temperature was raised to 120 to 130 ℃. Subsequently, 4.96 parts by mass of the (meth) acrylic monomer mixture described in table 1, (2-ethylhexanoyl) (tert-butyl) peroxide, and 0.5 part by mass of 1-dodecanethiol were added dropwise over 4 to 6 hours. Thereafter, 0.07 part by mass of benzoyl peroxide tert-butyl ester was added thereto, and the mixture was allowed to stand at 120 to 130 ℃ for 2 hours to obtain a (meth) acrylic modified polyester resin (1) solution containing 70.5 mass% of nonvolatile components. The (meth) acrylic modified polyester resin (1) solution had a number average molecular weight (Mn) of 2,942, a weight average molecular weight (Mw) of 8,468, an acid value of 11mgKOH/g, a hydroxyl value (solid content) of 141mgKOH/g, and a Gardner viscosity of Z1 to Z2.
( Example 2: preparation of (meth) acrylic-modified polyester resin (2) )
15.76 parts by mass of the saturated polyester resin (2) solution obtained in production example 2, 5.22 parts by mass of glycidyl neodecanoate, and 26.25 parts by mass of butyl acetate were charged into a reaction vessel equipped with a stirrer, a condenser, and a thermometer, and the temperature was raised to 120 to 130 ℃. Subsequently, 4.02 parts by mass of the (meth) acrylic monomer mixture shown in Table 1 and (2-ethylhexanoyl) (tert-butyl) peroxide were added dropwise over 4 to 6 hours. Thereafter, 0.07 part by mass of benzoyl peroxide tert-butyl ester was added thereto, and the mixture was allowed to stand at 120 to 130 ℃ for 2 hours to obtain a (meth) acrylic modified polyester resin (2) solution containing 72.3 mass% of nonvolatile components. The (meth) acrylic modified polyester resin (2) solution had a number average molecular weight (Mn) of 2,593, a weight average molecular weight (Mw) of 6,660, an acid value of 15.2mgKOH/g, a hydroxyl value (as a solid content) of 143mgKOH/g, and a Gardner viscosity of Z4 to Z5.
( Example 3: preparation of (meth) acrylic-modified polyester resin (3) )
18.30 parts by mass of the saturated polyester resin (3) solution obtained in production example 3 and 21.26 parts by mass of butyl acetate were charged into a reaction vessel equipped with a stirrer, a condenser and a thermometer, and the temperature was raised to 120 to 130 ℃. Subsequently, 4.89 parts by mass of the (meth) acrylic monomer mixture described in table 1, (2-ethylhexanoyl) (tert-butyl) peroxide, and 0.5 part by mass of 1-dodecanethiol were added dropwise over 4 to 6 hours. Thereafter, 0.07 part by mass of benzoyl peroxide tert-butyl ester was added thereto, and the mixture was allowed to stand at 120 to 130 ℃ for 2 hours to obtain a (meth) acrylic modified polyester resin (3) having a nonvolatile content of 76.5 mass%. The (meth) acrylic modified polyester resin (3) solution had a number average molecular weight (Mn) of 2,363, a weight average molecular weight (Mw) of 6,873, an acid value of 11.2mgKOH/g, a hydroxyl value (as a solid content) of 140mgKOH/g, and a Gardner viscosity of Z-Z1.
( Example 4: preparation of (meth) acrylic-modified polyester resin (4) )
22.05 parts by mass of the saturated polyester resin (4) solution obtained in production example 4, 12.88 parts by mass of butyl acetate, and 19.24 parts by mass of propylene glycol monomethyl ether acetate were charged into a reaction vessel equipped with a stirrer, a condenser, and a thermometer, and the temperature was raised to 120 to 130 ℃. Subsequently, 3.15 parts by mass of the (meth) acrylic monomer mixture described in table 1, (2-ethylhexanoyl) (t-butyl) peroxide, and 0.45 part by mass of 1-dodecanethiol were added dropwise over 4 to 6 hours. Thereafter, 0.06 part by mass of benzoyl peroxide tert-butyl ester was added thereto, and the mixture was allowed to stand at 120 to 130 ℃ for 2 hours to obtain a (meth) acrylic modified polyester resin (4) solution containing 65% by mass of nonvolatile components. The (meth) acrylic modified polyester resin (4) solution had a number average molecular weight (Mn) of 3,172, a weight average molecular weight (Mw) of 8,126, an acid value of 7.5mgKOH/g, a hydroxyl value (as a solid content) of 77.4mgKOH/g, and a Gardner viscosity of L.
( Example 5: preparation of (meth) acrylic-modified polyester resin (5) )
25.25 parts by mass of the saturated polyester resin (5) solution obtained in production example 5, 17.04 parts by mass of butyl acetate, and 3.01 parts by mass of propylene glycol monomethyl ether acetate were charged into a reaction vessel equipped with a stirrer, a condenser, and a thermometer, and the temperature was raised to 120 to 130 ℃. Subsequently, 3.94 parts by mass of the (meth) acrylic monomer mixture described in table 1, (2-ethylhexanoyl) (tert-butyl) peroxide, and 0.54 part by mass of 1-dodecanethiol were added dropwise over 4 to 6 hours. Thereafter, 0.07 part by mass of benzoyl peroxide tert-butyl ester was added thereto, and the mixture was allowed to stand at 120 to 130 ℃ for 2 hours to obtain a (meth) acrylic modified polyester resin (5) solution having a nonvolatile content of 73.7% by mass. The (meth) acrylic modified polyester resin (5) solution had a number average molecular weight (Mn) of 2,144, a weight average molecular weight (Mw) of 7,441, an acid value of 7.4mgKOH/g, a hydroxyl value (solid content) of 80.6mgKOH/g, and a Gardner viscosity of V-W.
The compositions of the (meth) acrylic modified polyester resins (1) to (5) obtained in examples 1 to 5 are shown in table 1.
[ Table 1]
( Comparative production example 1: preparation of acrylic resin solution (C1-1) )
Butyl acetate was put into a reaction vessel equipped with a stirrer, a condenser and a thermometer, and the temperature was raised to 120 to 130 ℃. Subsequently, the acrylic monomer mixture used in example 5 was added dropwise over 4 to 6 hours. Thereafter, benzoyl peroxide tert-butyl peroxide was added thereto, and the mixture was allowed to stand at 120 to 130 ℃ for 2 hours to obtain an acrylic resin solution (C1-1) having a nonvolatile content of 70.8 mass%. The acrylic resin solution (C1-1) had a number average molecular weight (Mn) of 2,742, a weight average molecular weight (Mw) of 7, 841, an acid value of 6.6mgKOH/g, a hydroxyl value (as a solid content) of 73.3mgKOH/g, and a Gardner viscosity of Y-Z.
( Comparative example 1: preparation of Mixed solution (C1) of acrylic resin and polyester resin )
The acrylic resin solution (C1-1) obtained in comparative production example 1 and the saturated polyester resin (5) solution obtained in production example 5 were mixed at 25 ℃ so that the amount of polyester was the same as in example 5, to obtain a mixed solution (C1) of an acrylic resin and a polyester resin.
( Comparative example 2: preparation of (meth) acrylic modified polyester resin (C2) )
46.7 parts by mass of the saturated polyester resin (6) solution obtained in production example 6, 1.41 parts by mass of butyl acetate, and 12.7 parts by mass of propylene glycol monomethyl ether acetate were charged into a reaction vessel equipped with a stirrer, a condenser, and a thermometer, and the temperature was raised to 120 to 130 ℃. Subsequently, 2.39 parts by mass of the (meth) acrylic monomer mixture described in table 2, (2-ethylhexanoyl) (t-butyl) peroxide, and 0.27 part by mass of 1-dodecanethiol were added dropwise over 4 to 6 hours. Thereafter, 0.05 part by mass of benzoyl peroxide tert-butyl ester was added thereto, and the mixture was allowed to stand at 120 to 130 ℃ for 2 hours, but the solution was separated into 2 layers, and the intended (meth) acrylic modified polyester resin solution was not obtained.
[ Table 2]
Example 6 preparation of white paint (1)
26.4 parts by mass of the (meth) acrylic modified polyester resin (4) solution obtained in example 4, 34.3 parts by mass of titanium oxide ("Ti-Pure R960" manufactured by Dupont Co., ltd., silica ("AEROSIL R972") 0.3 parts by mass, and 4.1 parts by mass of a mixed solvent obtained by mixing an aromatic solvent ("Solvesso 100" manufactured by Exxon Mobil Co., ltd.) and propylene glycol monomethyl ether acetate at a mass ratio of 7:3 were mixed in a reaction vessel equipped with a stirrer, a condenser and a thermometer, and dispersed until the particle diameter became 10 μm or less, and then, A white paint (1) was obtained by adding 26.4 parts by mass of a (meth) acrylic modified polyester resin (4) solution, 6.1 parts by mass of an amino resin ("Cymel 303LF" manufactured by Allnex corporation), 0.6 parts by mass of a catalyst ("Nacure 5225" manufactured by King corporation), 0.3 parts by mass of a matting agent ("Syloid ED 3" manufactured by Allnex corporation), 0.5 parts by mass of a leveling agent ("Modaflow 2100" manufactured by Allnex corporation), and 1.0 part by mass of a mixed solvent in which an aromatic solvent ("Solvesso 100" manufactured by Exxon Mobil corporation) and propylene glycol monomethyl ether acetate were mixed at a mass ratio of 7:3, and adjusting the mixed solvent so that the viscosity of Forster cup #4 at 25 ℃ became about 100 seconds.
Example 7 preparation of white paint (2)
A white paint (2) was obtained in the same manner as in example 6, except that the (meth) acrylic modified polyester resin (5) solution obtained in example 5 was used in place of the (meth) acrylic modified polyester resin (4) solution used in example 6.
Comparative example 3 preparation of white paint (3)
A white paint (3) was obtained in the same manner as in example 6, except that the mixed solution (C1) of the acrylic resin and the polyester resin obtained in comparative example 1 was used in place of the solution of the (meth) acrylic modified polyester resin (4) used in example 6.
Comparative example 4 preparation of white paint (4)
A white paint (4) was obtained in the same manner as in example 6 except that a saturated polyester resin solution ("BECKOLITE GS-13" manufactured by DIC) was used in place of the (meth) acrylic modified polyester resin (4) solution used in example 6.
Comparative example 5 preparation of white paint (5)
A white coating (5) was obtained in the same manner as in example 6 except that a saturated polyester resin solution ("BECKOLITE GS-37-1" available from DIC corporation) was used in place of the (meth) acrylic modified polyester resin (4) solution used in example 6.
Comparative example 6 preparation of white paint (6)
A white paint (6) was obtained in the same manner as in example 6, except that the acrylic resin solution (C1-1) obtained in comparative production example 1 was used instead of the (meth) acrylic modified polyester resin (4) solution used in example 6.
Comparative example 7 preparation of white paint (7)
A white paint (7) was obtained in the same manner as in example 6 except that a saturated polyester resin solution ("BECKOLITE GS-12" manufactured by DIC) was used in place of the (meth) acrylic modified polyester resin (4) solution used in example 6.
Coated steel sheets were produced using the white paints obtained in the above examples and comparative examples.
Examples 8 and 9 production of coated Steel sheets (A) and (B)
The white paints (1) and (2) obtained in examples 5 and 6 were each coated on hot-dip zinc-chromate-treated steel sheets having a thickness of 0.5mm by a hard coater so that the thickness became 15 to 20 μm, and were dried by heating in an oven at 250 ℃ for 20 seconds (the peak metal temperature was 210 ℃) to obtain coated steel sheets (A) and (B).
Comparative examples 8 to 11 production of coated Steel sheets (C) to (F)
The white paints (3) to (6) obtained in comparative examples 3 to 6 were applied to hot-dip zinc chromate-treated steel sheets having a thickness of 0.5mm by a hard coater so that the film thickness became 15 to 20 μm, and were dried by heating in an oven at 230 ℃ for 40 seconds (the peak metal temperature was 230 ℃) to obtain coated steel sheets (C) to (F).
( Examples 10 and 11: production of < primer layer > coated Steel sheets (G) and (H) )
As the primer layer, a saturated polyester resin ("BECKOLITE GS-12" manufactured by DIC corporation) was coated on a hot-dip zinc-chromate-treated steel sheet having a thickness of 0.5mm by a hard coater so that the thickness became 5 μm, and was dried by heating in an oven at 250 ℃ for 20 seconds (metal peak temperature: 210 ℃ C.) to form a primer layer, and then, the white paints (1) and (2) obtained in examples 5 and 6 were coated on the surface of the primer layer by a hard coater so that the thickness became 15 μm, and were dried by heating in an oven at 250 ℃ for 40 seconds (metal peak temperature: 210 ℃ C.) to prepare coated steel sheets (G) and (H).
( Comparative examples 12 to 14: production of coated Steel sheets (I) to (K) < primer layer > )
As the primer layer, saturated polyester resin ("BECKOLITE GS-12" manufactured by DIC corporation) was coated on a hot-dip zinc-chromate-treated steel sheet having a thickness of 0.5mm by a hard coater so as to have a film thickness of 5 μm, and heat-dried in an oven at 250 ℃ for 20 seconds (metal peak temperature: 210 ℃) to form a primer layer, and then, the white paints (3), (6) and (7) obtained in comparative examples 3, 6 and 7 were coated on the surface of the primer layer by a hard coater so as to have a film thickness of 15 μm, and heat-dried in an oven at 250 ℃ for 40 seconds (metal peak temperature: 230 ℃) to prepare coated steel sheets (I) to (K).
The coated steel sheets obtained in the above examples and comparative examples were used to perform the following evaluations.
[ method for measuring Pencil hardness ]
The hardness of the coated surfaces of the coated steel sheets (A) to (K) was measured by the method according to EN 13523-4.
[ method for measuring gloss ]
The gloss of the coated surfaces of the coated steel sheets (A) to (K) was measured by the method according to EN 13523-2, and the 60 ℃ reflectance of the coated surfaces was measured.
[ method for evaluating workability (crack-free test) ]
The flexibility of the coating film was evaluated by a T-bend test. Specifically, according to EN 13523-7, the coated steel sheets (a) to (K) obtained in the past were bent at 180 °, and cracks occurring in the bent portions were observed with a magnifying glass of 10 times. The minimum value at which no crack occurs at the bent portion was evaluated by setting 0T when the coated steel sheet was bent 180 ° without any object being held at the bent portion and setting (X/2) T when the coated steel sheet was bent while holding X sheets of the same thickness as the coated steel sheet at the bent portion.
[ method for evaluating processability (tape test) ]
The flexibility of the coating film was evaluated by a T-bend test. Specifically, according to EN 13523-7, the coated steel sheets (a) to (K) obtained in the past were bent at 180 °, and a pressure-sensitive adhesive tape made of nicolban co. The minimum value at which peeling does not occur was evaluated by 0T when the coated steel sheet was bent 180 ° without any object being held at the bent portion, and (X/2) T when the coated steel sheet was bent with X sheets of the same thickness as the coated steel sheet held at the bent portion.
[ method for evaluating weather resistance ]
The weather resistance test was carried out using a QUV accelerated weathering tester manufactured by Q-Lab corporation. Specifically, the coated steel sheets (Sup>A) to (K) obtained above were kept at 60 ℃ for 4 hours while UV irradiation (UV-Sup>A lamp) was performed, and then subjected to Sup>A weather resistance test for 2000 hours at 50 ℃ with 4-hour cycles under wetting, and evaluated for gloss retention on the coating film surface.
[ method for evaluating stain resistance ]
About 2ml of a 10% carbon black aqueous dispersion was dropped on the coated steel sheets (a) to (K) obtained above, and after drying at 80 ℃ for 24 hours, the coated steel sheets were wiped with a pad soaked with water, and evaluated according to the following criteria.
O: no trace remained on the surface of the coated steel sheet.
And (delta): traces remained on the surface of the coated steel sheet.
X: traces remained on the surface of the coated steel sheet.
The evaluation results of the coated steel sheets (a) to (F) produced in examples 8 and 9 and comparative examples 8 to 11 are shown in table 3.
[ Table 3]
The evaluation results of the coated steel sheets (G) to (K) produced in examples 10 and 11 and comparative examples 12 to 14 are shown in table 4.
[ Table 4]
Example 12 preparation of clear coating (1)
To a reaction vessel equipped with a stirrer, a condenser and a thermometer, 87.8 parts by mass of the (meth) acrylic modified polyester resin (5) solution obtained in example 5, 10.0 parts by mass of an amino resin ("Cymel 303LF" manufactured by Allnex corporation), 0.9 part by mass of a catalyst ("Nacure 5225" manufactured by King corporation), 0.5 part by mass of a leveling agent ("Modaflow 2100" manufactured by Allnex corporation), an aromatic solvent ("Solvesso 100" manufactured by Exxon Mobil corporation) and propylene glycol monomethyl ether acetate were charged such that 7:3 was mixed with 0.8 part by mass of a mixed solvent, and the viscosity of ford cup #4 at 25 ℃ was further adjusted to about 100 seconds, thereby obtaining a clear coating (1).
Example 13 production of coated Steel sheet (L)
The clear coating (1) obtained in example 12 was applied to a hot-dip zinc chromate-treated steel sheet having a thickness of 0.5mm by a hard coating machine so that the thickness thereof became 15 to 20 μm, and the steel sheet was dried by heating in an oven at 250 ℃ for 20 seconds (peak metal temperature: 210 ℃) to obtain a coated steel sheet (L).
[ Table 5]
Examples 8 and 9 shown in Table 3 are examples of white paints using the (meth) acrylic modified polyester resin of the present invention, and it was confirmed that the paints had nonvolatile contents each of which was 73.3 mass% or less, and had high solids. Further, it was confirmed that the coating film of the white paint was excellent not only in processability and weather resistance but also in hardness and stain resistance.
On the other hand, comparative example 8 is an example of a white paint using a mixed solution of an acrylic resin and a polyester resin, and it was confirmed that although a paint having a high nonvolatile content and a high solid content could be produced, the gloss retention of the coating film of the paint was as low as 60%, and the weather resistance was insufficient.
Comparative examples 9 and 10 are examples of white paints using a saturated polyester resin, and it was confirmed that the nonvolatile content was as low as 64.3 mass% (comparative example 9) and 63.2 mass% (comparative example 10), and that a high-solid paint could not be produced. In addition, it was confirmed that the gloss retention of the coating film of the white paint was extremely low at 30% (comparative example 9) and 55% (comparative example 10), and the weather resistance was remarkably insufficient.
Comparative example 11 is an example of a white paint using an acrylic resin solution, and it was confirmed that although a high-solid paint having a high nonvolatile content could be produced, the paint film of the paint had insufficient processability.
Examples 10 and 11 and comparative examples 12 to 14 shown in table 4 are coated steel sheets in which a primer layer is provided between the steel sheet and a white paint. The white paint films of the coated steel sheets obtained in examples 10 and 11 were confirmed to have excellent workability and weather resistance, and also excellent film hardness and stain resistance.
Example 13 shown in table 5 is an example of a clear coating material using the (meth) acrylic modified polyester resin of the present invention. The clear coating film of the coated steel sheet obtained in example 13 was found to have excellent workability and weather resistance, and also excellent coating film hardness and stain resistance.
Claims (11)
1. A (meth) acrylic modified polyester resin characterized in that a saturated polyester resin (A) and a (meth) acrylic monomer mixture (B) containing a hydroxyl group-containing (meth) acrylic monomer are used as essential reaction raw materials,
the saturated polyester resin (A) is a polycondensate of an aliphatic diol (a 1) and a dicarboxylic acid (a 2) containing an aliphatic dicarboxylic acid,
the aliphatic diol (a 1) comprises one or more selected from the group consisting of 2-butyl-2-ethyl-1,3-propanediol, 2-methyl-1,4-butanediol, 2-ethyl-1,4-butanediol, 2-methyl-1,3-propanediol, 3-methyl-1,5-pentanediol, 3-methyl-1,5-heptanediol,
the content of the aliphatic dicarboxylic acid in the dicarboxylic acid (a 2) is 5% by mass or more.
2. The (meth) acrylic modified polyester resin according to claim 1, wherein the mass ratio [ (a)/(B) ] of the saturated polyester resin (a) to the (meth) acrylic monomer mixture (B) is in the range of 15/85 to 50/50.
3. The (meth) acrylic modified polyester resin according to claim 1 or 2, wherein the aliphatic diol (a 1) further comprises a linear diol having no side chain.
4. The (meth) acrylic modified polyester resin according to claim 1 or 2, wherein the content of the aliphatic dicarboxylic acid is in the range of 10 to 20% by mass in the dicarboxylic acid (a 2).
5. The (meth) acrylic modified polyester resin according to claim 1 or 2, wherein the saturated polyester resin (a) has a weight average molecular weight in the range of 1000 to 5000.
6. The (meth) acrylic modified polyester resin according to claim 1 or 2, wherein the (meth) acrylic monomer mixture (B) contains 10% by mass or more of the hydroxyl group-containing (meth) acrylic monomer.
7. The (meth) acrylic modified polyester resin according to claim 1 or 2, wherein the weight average molecular weight of the (meth) acrylic modified polyester resin is in the range of 5000 to 20000.
8. The (meth) acrylic modified polyester resin according to claim 1 or 2, wherein the hydroxyl value of the (meth) acrylic modified polyester resin is in the range of 60 to 150.
9. A curable resin composition comprising the (meth) acrylic modified polyester resin according to any one of claims 1 to 8, a curing agent, and an organic solvent.
10. A coating material comprising the curable resin composition according to claim 9, wherein the nonvolatile content of the curable resin composition is 65% by mass or more.
11. A coated steel sheet having a cured coating film of the coating material according to claim 10.
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| JP2000327727A (en) * | 1999-03-16 | 2000-11-28 | Toyo Ink Mfg Co Ltd | Polyester-modified resin and resin composition using the resin and cured product using the resin |
| JP2012184370A (en) * | 2011-03-08 | 2012-09-27 | Toyo Ink Sc Holdings Co Ltd | Aqueous coating composition, and method for manufacturing the same |
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| JP2000327727A (en) * | 1999-03-16 | 2000-11-28 | Toyo Ink Mfg Co Ltd | Polyester-modified resin and resin composition using the resin and cured product using the resin |
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|---|---|
| WO2019102626A1 (en) | 2019-05-31 |
| DE112017008223T5 (en) | 2020-08-06 |
| JPWO2019102626A1 (en) | 2020-07-02 |
| CN111448229A (en) | 2020-07-24 |
| JP6725895B2 (en) | 2020-07-22 |
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